6-hydroxypyrid-2-one azo dyestuffs

ABSTRACT

A dyestuff of the formula ##SPC1## 
     Wherein m is 1, 2 or 3; R 9  is ##SPC2## 
     Wherein n is 0 or 1 and R&#34; is hydrogen or lower alkyl or ##SPC3## 
     Wherein p is 1, 2 or 3; R 10  is C 1   -6  alkyl, benzyl, sulphobenzyl, phenyethyl, sulphophenylethyl, ##EQU1## wherein r is 2 to 6, ##SPC4## 
     Or ##SPC5## 
     Wherein R&#34; has the meaning given above and the dyestuff as a whole contains only one group represented by Z, and Z is a cellulose-reactive group. The dyestuff is useful in dyeing and printing cellulose, polyamide and wool textile materials. Textile dyes with the above dyestuff exhibits good fastness to washing and to bleaching and good resistance to acids and alkalies.

This is a Continuation-in-Part of our earlier application Ser. No.238,620 filed March 27, 1972, now abandoned.

This invention relates to new azo dyestuffs of the 6-hydroxypyrid-2-oneseries.

The new dyestuffs are characterized by presence in the molecule of thefollowing structural element: ##SPC6##

Wherein one of T¹ and T² is CH₂, and the other forms a chain of 2 to 4carbon atoms, which may be part of a further ring system, the propertiesof the dyestuff being determined by the substituents attached to thethree free valencies depicted, as well as T¹ and T².

As a general rule, the more readily available new dyestuffs can berepresented by the general formula: ##SPC7##

Wherein R represents an aromatic radical, R¹ represents H, NH₂ or analkyl, aralkyl, cycloalkyl, aryl or heterocyclic group which may besubstituted, and T¹ and T² have the meanings stated above.

The present specification is particularly concerned with dyestuffs ofthe above type which also contain at least one sulphonic acid group andone or more cellulose reactive groups. Such dyes can be used as reactivedyes for silk, wool, nylon, natural or regenerated cellulose fibrousmaterials.

T¹ and T² together may represent any group of atoms having a chain of 3,4 or 5 carbon atoms connected to the pyridine nucleus through at leastone terminal CH₂ group. As examples of such groups, there may bementioned alkylene radicals, e.g. 1,3-trimethylene, 1,4-tetramethyleneand 1,5-pentamethylene which may be substituted, provided that oneterminal methylene group is left, e.g. by methyl or by a further,preferably homocyclic, ring system fused across adjacent carbon atoms ofT¹ and T², e.g. a 2,ω-tolylene, ω,ω'-o-xylylene, 2,ω-ethylphenylene ofthe formulae: ##SPC8##

In general, it is preferred that T¹ and T² together represent --(CH₂)₃-- or, more especially, --(CH₂)₄ --.

The alkyl group represented by R¹ in formula (2) may be of any lengthbut is preferably one of those containing up to 6 carbon atoms, e.g.methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, β-aminoethyl,γ-dimethylaminopropyl, β-(pyridinium-1-yl)ethyl and the alkyl group maybear a cellulose reactive substituent.

As examples of aralkyl groups represented by R¹ there may be mentioned:benzyl, and β-phenylethyl, which may bear a cellulose reactivesubstituent.

As an example of cycloalkyl groups represented by R¹ there may bementioned cyclohexyl and 2-methyl cyclohexyl.

As examples of aryl or substituted aryl radicals represented by R¹ theremay be mentioned more especially redicals of the benzene series in whichthe benzene ring or rings may be substituted, e.g. by chlorine, bromine,methyl, ethyl, nitro, carboxylic acid, sulphonic acid, aminosulphonyl,amino, acylamino and azinylamino groups in which the acyl or azinylgroups may be cellulose-reactive.

As examples of heterocyclic or substituted heterocyclic groupsrepresented by R¹ there may be mentioned, more particularly, 5- and6-membered monocyclic heterocyclic radicals, which may be substituted,e.g. pyrid-2-yl, thiazol-2-yl, piperidin-1-yl, and morpholin-1-yl.

The aromatic radical which is represented by R may be any aromaticcarbo- or hetero-cyclic radical which may carry substituents, e.g.,alkyl, cycloalkyl or aralkyl, alkoxy, aralkoxy, aryloxy, acyloxy,benzeneazo, naphthylazo, amino, alkylamino, dialkylamino, arylamino,N-alkylarylamino, aralkylamino, acylamino, carboxylic acid,aminocarbonyl and its N-substituted derivatives, alkoxycarbonyl,aminosulphonyl and its N-substituted derivatives, alkyl sulphonyl,alkylthio, aralkylthio, nitro, cyano, trifluoromethyl, sulphonic acidgroups and halogen atoms; also cellulose reactive groups.

As examples of cellulose-reactive groups, there may be mentioned vinylsulphone and aliphatic sulphone groups which contain a halogen atom orsulphate ester groups in β-position to the sulphur atom, e.g.β-chloroethyl- or β-sulphatoethylsulphone andβ-sulphatoethylsulphonylamino groups, α,β-unsaturated acyl radicals ofaliphatic carboxylic acids for example, acrylic acid, α-chloro-acrylicacid, propiolic acid, maleic acid and mono- and dichloro- maleic acids;also the acyl radicals of acids which contain a substituent which reactswith cellulose or polyamides in the presence of an alkali, e.g. theradical of a halogenated aliphatic acid such as chloroacetic acid,β-chloro and β-bromo-propionic acids and α,β-dichloro- and -dibromo-propionic acids. Other examples of cellulose or polyamide -- reactivegroups are tetrafluoro cyclo butane carbonyl, trifulorocyclo butenecarbonyl, tetrafluorocyclobutylethenyl carbonyl,trifluorocyclobutaneethenylcarbonyl, and heterocyclic radicals whichcontain 2 or 3 nitrogen atoms in the heterocyclic ring and at least onecellulose- or polyamide- reactive substituent on a carbon atom of thering.

As examples or such heterocyclic radicals, there may be mentioned, forexample

2:3-dichloro-quinoxaline-5- or

--6-sulphonyl,

2:3-dichloro-quinoxaline-5- or -6-carbonyl,

2:4-dichloro-quinazoline-6- or -7- sulphonyl,

2:4:6-trichloro-quinazoline-7- or -8- sulphonyl,

2:4:7- or 2:4:8-trichloro-quinazoline-6-sulphonyl,

2:4-dichloro-quinazoline-6-carbonyl,

1:4-dichloro-phthalazine-6-carbonyl,

β(4:5-dichloro-pyridazon-1-yl)propionyl,

2:4-dichloro-pyrimidine-5-carbonyl,

1-(phenyl-4-carbonyl)-4:5-dichloro-pyridazone,

1-(phenyl-4-sulphonyl)-4:5-dichloro-pyridazone,

and, more particularly s-triazin-2-yl and pyrimidin-2-yl or --4-ylradicals which contain on at least one of the remaining 2,4- and6-positions, a bromine or, preferably, a chlorine atom, a sulphonic acidgroup, a thiocyanato group, an aryloxy or arylthio group containing anelectronegative substituent such as sulphophenoxy, sulphophenylthio,nitrosulphophenoxy, disulphophenoxy and sulphonaphthoxy, or a group ofthe formula: ##EQU2## wherein Y¹ represents a group of atoms necessaryto form a 5- or 6- membered heterocyclic ring which may carrysubstituents or form part of a fused ring system; or a quaternaryammonium or pyridinium group; or a group of the formula: ##EQU3##wherein R⁴ and R⁵ each represents the same or different alkyl,cycloalkyl, aryl or aralkyl group, or R⁴ and R⁵ together form, togetherwith the nitrogen atom, a 5- or 6- membered heterocyclic ring; or agroup of the formula: ##EQU4## wherein R⁶ and R⁷ may be the same ordifferent and each represents a hydrogen atom or an alkyl, aryl oraralkyl group.

In the cases where the pyrimidine ring or triazine ring carries only onesuch reactive substituent, the said ring may have a non-reactivesubstituent on the remaining carbon atoms.

By a non-reactive substituent there is meant a group which is bound by acovalent bond to a carbon atom of the triazine or pyrimidine nucleus,which covalent bond is not ruptured under the conditions used forapplication of the reactive dye.

As examples of such substituents, there may be mentioned, for example,primary amino and hydroxyl groups, also mono- or disubstituted aminogroups, etherified hydroxyl and etherified mercapto groups; in the caseof substituted amino groups, this class includes, for example, mono- anddi-alkylamino groups in which the alkyl groups preferably contain atmost 4 carbon atoms, and which may also contain substituents forexample, hydroxyl or alkoxy groups, and phenylamino and naphthylaminogroups preferably containing sulphonic acid substituents; in the case ofetherified hydroxyl and mercapto groups, this class includes, forexample, alkoxy and alkylthio groups preferably those of low molecularweight, i.e. having up to 4 carbon atoms and phenoxy, phenylthio,naphthoxy or naphthylthio groups; as particular examples of all theseclasses there may be mentioned for example:

methylamino,

ethylamino,

dimethylamino,

β-hydroxyethylamino,

di-(β-hydroxyethyl)-amino,

β-chloroethylamino,

cyclohexylamino,

anilino,

sulphophenylamino,

disulphophenylamino,

N-methylsulphophenylamino,

N-β-hydroxyethylsulphophenylamino,

mono-, di, and trisulphonaphthylamino,

sulpho-o-tolylamino,

carboxyphenylamino and sulphocarboxyphenylamino,

N-ω-sulphomethylphenylamino,

methoxy, ethoxy, and butoxy,

phenoxy, methylphenoxy and chlorophenoxy and phenylthio groups.

Chlorine atoms or cyano, nitro, carboxy and carbalkoxy groups in the5-position of a pyrimidyl radical come into the category of non-reactivesubstituents.

Thus, in formula (2) above, the symbol R may represent a radical of thebenzene or naphthalene series which contains cellulose-reactive groupbound directly in some cases to a nuclear carbon atom but more usuallyis bound to a nuclear carbon atom through a linking amino group. Typicalradicals include for example, not only phenyl or naphthyl, but alsostilbene, diphenyloxide, diphenylmethane, diphenylurea, diphencxyethane,and diphenylamine radicals, which contain at least one, and preferablytwo, sulphonic acid groups.

Alternatively, or in addition, a cellulose-reactive group may be presentas a substituent in R¹ of formula (2) especially where this representsan alkyl or benzyl radical.

Within the broad class of reactive dyes discussed above, the followingsub-class is especially preferred:

Dyestuffs of the formula: ##SPC9##

wherein

m is 1, 2 or 3

R⁹ is selected from the group consisting of ##SPC10##

where n is 0 or 1 and R¹¹ is H or lower alkyl

and ##SPC11##

where p is 1, 2 or 3;

R¹⁰ is selected from the group consisting of C₁₋₆ alkyl, benzyl,sulphobenzyl, phenylethyl, sulphophenylethyl, ##EQU5## where r is 2 to6, ##SPC12##

and ##SPC13##

R¹¹ has the meaning given above and the dyestuff as a whole containsonly one group represented by Z;

Z is a cellulose-reactive group selected from the group consisting of

2,3-dichloroquinoxalin-5-sulphonyl,

2,3-dichloroquinoxalin-5-carbonyl,

2,3-dichloroquinoxalin-6-sulphonyl,

2,3-dichloroquinoxalin-6-carbonyl,

2,4-dichloroquinazolin-6-sulphonyl,

2,4-dichloroquinazolin-6-carbonyl,

2,4-dichloroquinazolin-7-sulphonyl,

2,4,6-trichloroquinazolin-7-sulphonyl,

2,4,6-trichloroquinazolin-8-sulphonyl,

2,4,7-trichloroquinazolin-6-sulphonyl,

2,4,8-trichloroquinazolin-6 -sulphonyl,

1,4-dichlorophthalazin-6-carbonyl,

β(4,5-dichloropyridazon-1-yl)propionyl,

2,4-dichloropyrimidin-5-carbonyl,

4-(4',5'-dichloropyridazon-1yl)benzoyl,

4-(4',5'-dichloropyridazon-1yl)phenylsulphonyl,

2,4-dichloropyrimid-6-yl,

2,4,5-trichloropyrimid-6-yl,

2,4-dichloro-5-cyanopyrimid-6-yl,

2,4-difluoro-5-chloropyrimid-6-yl,

4-chloro-6-methyl-2-methylsulphonylpyrimid-4-yl,

2,4-dichloro-5-bromopyrimid-6-yl,

2,4-dichloropyrmmidin-5-sulphonyl,

2,2,3,3-tetrafluorocyclobutylcarbonyl,

2,3,3,-trifluorocyclobut-1-enyl carbonyl,

β-(2,2,3,3-tetrafluorocyclobutyl)acryloyl,

β-(2,3,3-trifluorocyclobut-1-enyl)acryloyl,

2-chlorobenzthiazol-6-carbonyl, ##EQU6## in which X is Cl, NH₂, loweralkoxy, phenoxy, sulphophenoxy, lower alkylamino, di(lower alkyl)amino,##SPC14##

and ##SPC15##

in which p is 1, 2 or 3, ##SPC16##

in which X¹ is CH₃, Cl, OCH₃ or CO₂ H and q is 1 or 2, ##SPC17##

in which q and X have the meanings stated above and ##EQU7## in which Aris the N,N'-divalent radical of a diamine selected from the groupconsisting of 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylsulphone,4,4'-diaminodiphenoxyethane 2,2'-disulphonic acid,2,6-naphthalene-4,8-disulphonic acid, benzidine-2,2'-disulphonic acid,4,4'-diaminodiphenylurea-2,2'-disulphonic acid,4,4'-diaminostilbene-2,2'-disulphonic acid,1,3-diaminobenzene-4,6-disulphonic acid and 4,4'-diaminodiphenylsulphide-2,2'acid -disulphonic aicd and D represents the radical of asecond monoazo entity defined by the removal of the group Z from thecompound represented by formula (22).

It will be appreciated that the preferred sub-class of dyestuffs asdefined above comprises two main types viz.

a. Dyestuffs of formula (22) in which R⁹ is of the structure ##SPC18##

where n, R¹¹ and Z have the meanings given above, in combination withR¹⁰ selected from C₁₋₆ alkyl benzyl, sulphobenzyl, phenylethyl orsulphophenylethyl and

b. Dyestuffs of formula (22) in which R⁹ is of the structure ##SPC19##

where p has the meaning given above, in combination with R¹⁰ selectedfrom ##EQU8## ##SPC20## where r, R¹¹ and Z have the meanings givenabove.

It will be further appreciated that the preferred sub-class of reactivedyes given above consists of monoazo dyes except in the case where Z is##EQU9## Ar and D having the meanings given above, in which case thedyestuffs contain two azo groups per molecule and are represented by thefollowing formula (23) and (24) corresponding to types (a) and (b)defined above, respectively. ##SPC21##

where Ar has the meaning given above and m, n, R¹⁰, R¹¹ have themeanings given for type (a) above. ##SPC22##

where Ar has the meaning given above and R¹² is selected from ##SPC23##

in which the --CH₂ group is joined to the nitrogen of the pyridone ringand m, r and p have the meaning given above for type (b).

The preferred sub-class of reactive dyes are characterized by acombination of extremely bright greenish or reddish yellow shades and,in some cases, very good fastness to bleach.

The new dyestuffs may be obtained by a variety of methods. In thegeneral case they may be obtained by coupling a diazotized aromaticamine or tetraazotized aromatic diamine containing such groups with acompound of the formula: ##SPC24##

wherein R¹, T¹ and T² have the meanings stated above and n is 0 or 1.

Compounds of formula (16) can be obtained by reacting a compound of theformula: ##EQU10## with cyanacetic ester and an amino compound offormula RNH₂ to form a compound of the formula: ##SPC25##

and subsequently heating in mineral acid e.g. 70-100% sulphuric acid,15-30% hydrochloric acid and syrupy phosphoric acid whereby the cyanogroup is converted to aminocarbonyl or replaced by a hydrogen atom. Thefollowing table names compounds of formula (17) together with thederived meaning of T¹ -- T² :

    2-ethoxycarbonyl-cyclopentanone                                                                    trimethylene                                             2-ethoxycarbonyl-cyclohexanone                                                                     tetramethylene                                           2-ethoxycarbonyl-cycloheptanone                                                                    pentamethylene                                           2-ethoxycarbonyl-α-tetralone                                                                 2,ω-ethylphenylene                                                      (formula 2c above)                                       3-ethoxycarbonyl-β-tetralone                                                                  ω,ω'-o-xylylene                                                   (formula 2b above)                                       6-ethoxycarbonylhydrindan-7-one                                                                    2,ω-tolylene                                                            (formula 2a above)                                   

As examples of aromatic amines and diamines which may be used, there maybe mentioned:

4-aminoazobenzene mono- and di-sulphonic acids,

4-amino-2-methyl-5-methoxyazobenzene-3'-sulphonic acid,

orthanilic, metanilic and sulphanilic acids,

2-, 3- and 4-aminobenzoic acids,

aniline-2,4-, -2,5- and -3,5-disulphonic acids,

2,5-dichloroaniline-4-sulphonic acid,

4-methoxy aniline-2- and -3-sulphonic acids,

2-methoxy aniline-5-sulphonic acid,

5-amino-2-hydroxy-3-sulphobenzoic acid,

4- and 5-acetylaminoaniline-2-sulphonic acids,

4- and 5-benzoylaminoaniline-2-sulphonic acids,

5-acetylamino-2-aminobenzoic acid,

4- and 5-(2',4'-dichloro-s-triazin-6'-ylamino)-aniline-2-sulphonic and2,5- and 2,4-disulphonic acids,

4- and 5-(2'-chloro-4'-amino-s-triazin-6'-ylamino)aniline-2-sulphonicand 2,5- and 2,4-disulphonic acids,

4- and 5-(2'-chloro-4'-metanilino-s-triazin-6'-ylamino)aniline-2-sulphonic and 2,5- and 2,4-disulphonic acids,

4- and 5-(2'-chloro-4'-sulpho-o-toluidino-s-triazin-6'-ylamino)aniline-2-sulphonic and 2,5- and 2,4-disulphonic acids,

chloro- and nitro-aniline sulphonic acids,

aniline-5-sulphonanilide-2-sulphonic acid,

aniline-5-sulphon-N- ethylanilide-2-sulphonic acid,

4-amino-4'-nitrodiphenylamine-2'-sulphonic acid,

4-amino-2'-nitrodiphenylamine-4'-sulphonic acid,

1-aminonaphthalene-3-,4-, -5-, -6-, 7- and 8-sulphonic acids,

2-aminonaphthalene-1-, -4-, -5-, -6-, -7- and -8- sulphonic acids,

1-aminonaphthalene-aminonaphthalene-2,7-, 3,6-, 3,8-, 4,6- and 4,7-disulphonic acids,

2-aminonaphthalene-1,5-, -3,6-, -4,8-, -5,7- and -6,8-disulphonic acids,

1- and 2-aminonaphthalene trisulphonic acids,

4-nitro-4'-aminostilbene-2,2'-disulphonic acid,

4- and 5- sulpho-2-aminobenzoic acids,

6-chloro-, 6-nitro- and 6-acetylamino-2-aminophenol-4-sulphonic acids,

2-aminophenol-4- and -5-sulphonic acids and 4,6-disulphonic acid,

3-amino-3-hydroxy-6-sulphobenzoic acid,

4-chloro- and 4-nitro-2-aminophenol-6-sulphonic acids,

1-amino-2-hydroxynaphthalene-4-sulphonic acid,

6-nitro-1-amino-2-hydroxynaphthalene-4-sulphonic acid,

1,3-phenylene diamine -4,6- disulphonic acid,

1,4-phenylene diamine-2,5-disulphonic acid,

4,4'-diaminodiphenyl-2- and 3-sulphonic acids,

4,4'-diaminodiphenyl-2,2'- and -3,3'-disulphonic acids,

2,6-naphthylene diamine-1,5- and -3,7-disulphonic acids,

6-acetylamino-2-naphthylamine-4,8-disulphonic acid,

4,4'-diaminodiphenyl urea-2,2'-and 3,3'-disulphonic acids,

and 4,4'-diaminostilbene-2,2'-disulphonic acid.

The new dyestuffs wherein R or R¹ of formula (2) contains an acylaminogroup can, after hydrolysis to form an amino group, be converted to acellulose-reactive dyestuff by condensation with the anhydride or halideof an acid of which the acid radical contains a substituent capable ofchemically reacting with the fibre to form a chemical bond, or aheterocyclic compound which contains a halogen atom attached to a carbonatom of the heterocyclic nucleus and also a reactive substituent of thekind just stated.

As examples of halides or anhydrides of acids or heterocyclic compoundswhich may be used, there may be mentioned, for example, carbyl sulphateand the anhydrides or acid halides of α-β-unsaturated aliphatic acidssuch as chloromaleic anhydride, propiolyl chloride and acryloylchloride, the acid chlorides of halogenated aliphatic acids e.g.

chloroacetyl chloride,

sulphochloroacetyl chloride,

β-bromo and β-chloro-propionyl chlorides,

α-β-dichloro and-dibromo-propionyl chlorides,

2,2,3,3-tetrafluorocyclobutane carbonyl chloride,

β-(2,2,3,3-tetrafluorocyclobutyl)acryloyl chloride,

2,3,3-trifluorocyclobut-1-ene carbonyl chloride,

β-(2,3,3-trifluorocyclobut-1-enyl)acrylyl chloride,

also heterocyclic compounds which contain at least 2 nitrogen atoms inthe heterocyclic rings and which contain 2 or more halogen, especiallychlorine atoms in the ortho positions to the nitrogen atoms, e.g.

2:3-dichloro-quinoxaline-5- and -6- carbonyl chlorides,

2:3-dichloroquinoxaline-5- and -6- sulphonyl chlorides,

2:4-dichloro-quinazoline-6- and 7- sulphonyl chlorides,

2:4:6-trichloro-quinazoline-7- and 8-sulphonyl chlorides,

2:4:7- and 2:4:8-trichloro-quinazoline-6-sulphonyl chlorides,

2:4-dichloro-quinazoline-6-carbonyl chloride,

1:4-dichloro-phthalazin-6-carbonyl chloride,

2:4-dichloro-pyrimidine-5-carbonyl chloride,

β-(4:5-dichloro-pyridazonyl-1-)-propionyl chloride,

1-(4'-chloroformylphenyl)-4:5-dichloro-6-pyridazone,

1-4'-chlorosulphonylphenyl-4:5-dichloro-6-pyridazone,

2:4:6-tribromo and trichloro-pyrimidines,

2:4:5:6-tetrachloropyrimidine,

5-methyl-2-:4:6-trichloropyrimidine,

5-nitro-2:4:6-trichloropyrimidine,

2:4-dichloro-5-nitro-6-methyl-pyrimidine,

2:4-dichloro-5-nitropyrimidine,

2:4:6-trichloro-5-cyanopyrimidine,

5-ethoxycarbonyl-2:4-dichloropyrimidine,

2:4-dichloropyrimidine-5-carbonyl chloride,

cyanuric bromide,

cyanuric chloride:

also the primary condensation products of cyanuric bromide or cyanuricchloride with ammonia, an alkali metal sulphite or thiocyanate or anorganic mercaptan, hydroxy compound or an organic primary or secondaryamine, for example:

methanol,

ethanol,

iso-propanol,

phenol,

o-, m- and p-chlorophenols,

o-, m- and p-cresols,

o-, m- and p-sulphopenols,

thiophenol,

thioglycollic acid,

di-methyldithiocarbamic acid,

mercaptobenzthiazole,

thioacetamide,

methyl-,

dimethyl-,

ethyl-,

diethyl-,

n-propyl,

iso-propyl,

butyl-,

hexyl and cyclohexylamines,

toluidine,

piperidine,

morpholine,

methoxyethylamine,

ethanolamine,

aminoacetic acid,

aniline -2:4-,

2:5- and 3:5-disulphonic acids,

orthanilic,

metanilic and sulphanilic acids,

2-, 3- and 4- aminobenzoic acids,

4- and 5-sulpho2-aminobenzoic acids,

4- and 5- sulpho-o-toluidines,

5-amino-2-hydroxybenzoic acid,

2-amino-ethanesulphonic acid,

amino-naphthalene mono- and disulphonic acids and N-methylaminoethanesulphonic acid; also, the secondary condensation products of cyanuricchloride with:

alkali metal sulphites,

alkali metal thiocyanates

phenols and thiophenols

containing an electronegative substituent, and compounds of the formula:##EQU11## and ##EQU12## wherein Y¹, R⁴, R⁵, R⁶ and R⁷ have the meaningsstated above.

The cellulose-reactive dyes of formula (2) wherein thecellulose-reactive group is a s-triazine nucleus substituted by achlorine or bromine atom and an amino or substituted amino group canalso be obtained by reacting a cellulose-reactive dye of formula (2)containing a dichloro- or dibromo-s-triazine group with ammonia or anamine.

The cellulose-reactive dyes of formula (2) wherein thecellulose-reactive group is a s-triazine nucleus substituted by SO₃ H, aquaternary ammonium group or a group of formulae 3, 4 and 5, can beobtained by reacting a cellulose-reactive dye of formula (2) containinga s-triazine group substituted by at least one chlorine or bromine atomwith an alkali metal salt of sulphurous acid, a tertiary amine or acompound of formulae 19, 20 and 21.

The new dyestuffs containing sulphonic acid groups and a fibre-reactivegroup are valuable for the dyeing and printing of cellulose, polyamideand wool textile materials with which they react in the presence ofalkali and, if necessary, the action of heat. Textiles dyed with the newreactive dyes show good fastness to washing and in many cases, tobleaching treatments. They also show good resistance to acids andalkalies.

The invention is illustrated but not limited by the following Examplesin which parts are by weight and the ratio w/v is in the ratio of gramsto cc.:

EXAMPLE 1

2.68 parts of 1,3-phenylenediamine-4,6-disulphonic acid are dissolved in100 parts of water by adding 2N sodium carbonate solution until the pHis at 4-5. The solution is cooled to 0°-5° and added to a stirredsuspension of 1.95 parts of cyanuric chloride in a mixture of 10 partsof acetone, 40 parts of ice, 40 parts of water and one part of adispersing agent. The mixture is stirred at 0°-5° for 11/2 hours, the pHbeing maintained at 4-5 by the occasional addition of 2N sodiumcarbonate solution. 5 parts of hydrochloric acid (36°Tw) are added andthe solution is diazotized by the addition of a small excess of sodiumnitrite solution. Excess nitrous acid is decomposed by addition ofsulphamic acid solution.

2.36 parts of5-aminocarbonyl-3,4-tetramethylene-1-ethyl-6-hydroxypyrid-2-one aredissolved in 50 parts of water by addition of sodium carbonate solutionuntil the pH is 8-9. The solution is cooled to 0°-5°C and the solutionfrom paragraph 1 is added. The pH is slowly raised to 6-7 by addition ofsodium carbonate solution and the mixture is stirred at 0°-5°C, pH 6-7for 1 hour. A solution of 8 parts of disodium hydrogen phosphate and 4parts of potassium dihydrogen phosphate in 50 parts of water is addedand the dyestuff is precipitated by the addition of 10% w/v sodiumchloride. The precipitate is filtered off, washed with 50 parts of 10%brine solution, mixed with 1 part of disodium hydrogen phosphate and 0.5parts of potassium dihydrogen phosphate and dried in vacuo at roomtemperature. The product contains 1.8 moles of hydrolyzable chlorine perazo group and colors cellulosic fibres in conjunction with anacid-binding agent, in brilliant greenish-yellow shades which have goodfastness to light, washing, and bleaching treatments.

The 5-aminocarbonyl-3,4-tetramethylene-1-ethyl-6-hydroxypyrid-2-one usedin the above example can be obtained as follows:

A mixture of 28.2 parts of ethyl cyanoacetate, 42.5 parts of2-ethoxycarbonylcyclohexanone and 100 parts of 70% aqueous ethylamineare stirred at 60°-65°C for 16 hours, then evaporated in vacuo. Theresidue is suspended in 400 parts of water and extracted twice with 100parts of ether. The aqueous solution is treated with charcoal, filteredand acidified. The precipitate of5-cyano-3,4-tetramethylene-1-ethyl-6-hydroxypyrid-2-one is collected anddried. Found: m.p. 188°-190°C, C = 65.3; H = 6.9; N = 12.5%. C₁₂ H₁₄ O₂N₂ requires C = 66.0; H = 6.5; N = 12.8%.

9.2 parts of this product are dissolved in 54 parts of 96% sulphuricacid and the solution is stirred at 60°C for 12 hours, then poured intoice-water. The mixture is stirred for 2 hours, and the precipitate of5-aminocarbonyl-3,4-tetramethylene-1-ethyl-6-hydroxypyrid-2-onecollected and dried. Found: m.p. 124°-125°C. C = 59.6; H = 6.9; N =11.4%. C₁₂ H₁₆ O₃ N₂ requires C = 61.0; H = 6.8; N = 11.9%.

EXAMPLE 2

2.68 parts of 1,3-phenylenediamine-4,6-disulphonic acid are condensedwith 1.95 parts of cyanuric chloride and the product is diazotized asdescribed in Example 1.

2.22 parts of5-aminocarbonyl-3,4-trimethylene-1-ethyl-6-hydroxypyrid-2-one aredissolved in 50 parts of water by addition of sodium carbonate solutionuntil the pH is 8-9. The solution is cooled to 0°-5° and solution fromparagraph 1 is added. The pH is slowly raised to 6-7 by addition ofsodium carbonate solution and the mixture is stirred at 0°-5°, pH 6-7for 1/2 hour. 2.5 parts of 2-aminonaphthalene-5-sulphonic acid are addedand the mixture is stirred at 30°-40°C and pH 6-7 for 1 hour. It is thenheated to 50°-60°, salted to 20% w/v sodium chloride, cooled to 10° andthe product collected by filtration, washed with 50 parts of 20% brinesolution and dried in vacuo at 40°. The product contains 1.18 moles ofreactive chlorine per azo group and colors cellulose fibres when appliedin the presence of an acid binding agent in brilliant greenish-yellowshades having excellent fastness to light and washing treatments.

5-aminocarbonyl-3,4-trimethylene-1-ethyl-6-hydroxypyrid-2-one can beobtained as follows.

28.2 parts of ethyl cyanoacetate are added to 100 parts of 70% aqueousethylamine and the solution is stirred vigorously while 39 parts of2-ethoxycarbonylcyclopentanone are added. The mixture is stirred at60°-65° for 16 hours and then evaporated to dryness in vacuo. Theresidual syrup is suspended in 400 parts of water and extracted twicewith 100 parts of ether. The aqueous fraction is treated with charcoal,filtered and acidified to Congo Red with hydrochloric acid (36°Tw). Theprecipitate of 5-cyano-3,4-trimethylene-1-ethyl-6-hydroxypyrid-2-one iscollected and dried. Found: m.p. 234° (dec.), C = 63.9; H = 6.4; N =14.3%. C₁₁ H₁₂ O₂ N₂ requires C = 64.7; H = 5.9; N = 13.7%. 2.04 partsof this product are added to 25 parts of 96% sulphuric acid and thesolution is stirred for 16 hours at 50°-55° then poured into 200 partsof ice-water. The mixture is stirred for 2 hours at 0°-5° and theprecipitate of5-aminocarbonyl-3,4-trimethylene-1-ethyl-6-hydroxypyrid-2-one iscollected and dried in vacuo. Found: m.p. 187°-190°. C = 59.0; H = 6.4;N = 12.5%. C₁₁ H₁₄ O₃ N₂ requires C = 59.4; H = 6.35; N = 12.6%.

Further examples of the invention may be prepared by condensing thediamine listed in column II with one equivalent of the acylating agentlisted in column III, the product then being diazotized and coupled withthe coupling component in column IV in similar manner to Example 1.Column V describes the shade on cellulosic fibres when the dyestuff isapplied to the fibre in the presence of an acid-binding agent.

    I    II           III             IV               V                          Example                                                                            Diamine      Acylating agent Coupling Component                                                                             Shade                      __________________________________________________________________________    3    1,3-phenylenediamine-                                                                      2,4-dichloro-6-m-                                                                             1-ethyl-6-hydroxy-3,4-                                                                         Greenish-                       4-sulphonic acid                                                                           sulphoanilino-s-triazine                                                                      tetramethylenepyrid-2-one                                                                      yellow                     4    "            2,4-dichloro-6-[2',5'-                                                                        6-hydroxy-1-methyl-3,4-                                                                        "                                            disulphoanilino]-s-                                                                           trimethylenepyrid-2-one                                       triazine                                                    5    1,4-phenylenediamine-                                                                      2,4,6-trichloro-5-                                                                            6-hydroxy-1-n-propyl-3,4-                                                                      Reddish-                        2,5-disulphonic acid                                                                       cyanopyrimidine trimethylenepyrid-2-one                                                                        yellow                     6    1,4-phenylenediamine-                                                                      2,4-dichloro-6-N-w-                                                                           1-n-butyl-6-hydroxy-3,4-                                                                       "                               4-sulphonic acid                                                                           sulphomethylanilino-                                                                          pentamethylenepyrid-2-one                                     s-triazine                                                  7    1,3-phenylenediamine-                                                                      2,4,5,6-tetrachloro-                                                                          5-aminocarbonyl-1-benzyl-6-                                                                    Greenish-                       4,6-disulphonic acid                                                                       pyrimidine      hydroxy-3,4-tetramethylene-                                                                    yellow                                                       pyrid-2-one                                 8    "            2,4,6-trifluoro-5-                                                                            5-aminocarbonyl-2,6-dihydroxy-                                                                 "                                            chloropyrimidine                                                                              3,4-trimethylenepyridine                    9    "            4,5-dichloro-6-methyl-                                                                        "                "                                            2-methylsulphonyl                                                             pyrimidine                                                  10   "            2,4,6-trichloro 5-aminocarbonyl-1-ethyl-6-                                                                     "                                            pyrimidine      hydroxy-3,4-tetramethylene-                                                   pyrid-2-one                                 11   1,3-phenylenediamine-                                                                      5-bromo-2,4,6-  5-aminocarbonyl-1-ethyl-6-                                                                     Greenish-                       4,6-disulphonic acid                                                                       trichloropyrimidine                                                                           hydroxy-3,4-tetramethylene-                                                                    yellow                                                       pyrid-2-one                                 12   "            2,4-dichloropyrimidine-                                                                       "                "                                            5-carbonyl chloride                                         13   "            2,4-dichloropyrimidine-                                                                       "                "                                            5-sulphonyl chloride                                        14   "            tetrafluorocyclobutane                                                                        "                "                                            carbonyl chloride                                           15   "            trifluorocyclobutene                                                                          "                "                                            carbonyl chloride                                           16   "            β-(tetrafluorocyclobutyl)-                                                               "                "                                            acryloyl chloride                                           17   "            β-(trifluorocyclobutenyl)-                                                               "                "                                            acryloyl chloride                                           18   "            2-chlorobenzthiazole-                                                                         "                "                                            6-carbonyl chloride                                         19   "            2,4-dichloro-6-[6'-                                                                           1-ethyl-6-hydroxy-3,4-                                                                         "                                            sulphonaphthyl-2-amino]-                                                                      tetramethylenepyrid-2-one                                     s-triazine                                                  20   1,3-phenylenediamine-                                                                      2,4-dichloro-6-[5',7'-                                                                        5-aminocarbonyl-6-hydroxy-                                                                     Greenish-                       4,6-disulphonic acid                                                                       disulphonaphth-2-ylamino]-                                                                    1-methyl-3,4-tetramethylene-                                                                   yellow                                       s-triazine      pyrid-2-one                                 21   1,3-phenylenediamine-                                                                      2,4-dichloro-6-p-                                                                             1-isopropyl-6-hydroxy-3,4-                                                                     "                               4-sulphonic acid                                                                           sulphoanilino-s-triazine                                                                      tetramethylenepyrid-2-one                   22   "            2,4-dichloro-6-[2',5'-                                                                        1-n-propyl-6-hydroxy-3,4-                                                                      "                                            disulphoanilino]-s-                                                                           tetramethylenepyrid-2-one                                     triazine                                                    23   "            2,4-dichloro-6-[5'-                                                                           5-aminocarbonyl-1-ethyl-6-                                                                     "                                            sulphonaphth-1-ylamino]-                                                                      hydroxy-3,4-tetramethylene-                                   s-triazine      pyrid-2-one                                 24   1,3-phenylenediamine-                                                                      2,4-dichloro-6-[6'-                                                                           "                "                               4,6-disulphonic acid                                                                       sulphonaphth-1-ylamino]-                                                      s-triazine                                                  25   "            2,4-dichloro-6-[7'-                                                                           "                "                                            sulphonaphth-1-ylamino]-                                                      s-triazine                                                  26   4,6-diaminobenzene-                                                                        2,3-dichloroquinoxaline-                                                                      5-aminocarbonyl-6-hydroxy-                                                                     "                               1,3-disulphonic acid                                                                       5-sulphonyl chloride                                                                          1-methyl-3,4-tetramethylene-                                                  pyrid-2-one                                 27   "            2,3-dichloroquinoxaline-                                                                      "                "                                            6-sulphonyl chloride                                        28   4,6-diaminobenzene-                                                                        2,3-dichloroquinoxaline-                                                                      1-ethyl-6-hydroxy-3,4-                                                                         Greenish-                       1,3-disulphonic acid                                                                       5-carbonyl chloride                                                                           trimethylene-pyrid-2-one                                                                       yellow                     29   "            2,3-dichloroquinoxaline-                                                                      6-hydroxy-1-n-propyl-3,4-                                                                      4,6-diaminobenzene-                          6-carbonyl chloride                                                                           trimethylenepyrid-2-one                     30   "            2,4-dichloroquinazolin-                                                                       5-aminocarbonyl-6-hydroxy-                                                                     "                                            6-sulphonyl chloride                                                                          1-methyl-3,4-pentamethylene                                                   pyrid-2-one                                 31   "            2,4-dichloroquinazolin-                                                                       5-aminocarbonyl-1-ethyl-6-                                                                     "                                            7-sulphonyl chloride                                                                          hydroxy-3,4-pentamethylene                                                    pyrid-2-one                                 32   2,4-diaminobenzene                                                                         2,4,6-trichloroquinazolin-                                                                    6-hydroxy-1-(4'-sulphobenzyl)-                                                                 "                               sulphonic acid                                                                             7-sulphonyl chloride                                                                          3,4-tetramethylenepyrid-                                                      2-one                                       33   "            2,4,6-trichloroquinazolin-                                                                    6-hydroxy-1-(4'-sulphophenyl-                                                                  "                                            8-sulphonyl chloride                                                                          ethyl)-3,4-tetramethylene                                                     pyrid-2-one                                 34   4,6-diaminobenzene-                                                                        2,4,7-trichloroquinazolin-                                                                    1-n-butyl-6-hydroxy-3,4-                                                                       "                               1,3-disulphonic acid                                                                       6-sulphonyl chloride                                                                          tetramethylenepyrid-2-one                   35   "            2,4,8-trichloroquinazolin-                                                                    "                "                                            6-sulphonyl chloride                                        36   "            1,4-dichlorophthalazine-                                                                      1-ethyl-6-hydroxy-3,4-                                                                         "                                            6-carbonyl chloride                                                                           trimethylenepyrid-2-one                     37   2,4-diaminobenzene                                                                         1-(4'-chloroformylphenyl)-                                                                    6-hydroxy-1-(4'-sulphobenzyl)-                                                                 Greenish-                       sulphonic acid                                                                             4,5-dichloro-6-pyridazone                                                                     3,4-tetramethylenepyrid-2-one                                                                  yellow                     38   "            β-(4,5-dichloropyridazonyl-                                                              5-aminocarbonyl-6-hydroxy-1-                                                                   "                                            1-)propionyl chloride                                                                         (4'-sulphobenzyl)-3,4-                                                        tetramethylenepyrid-2-one                   39   "            1-(4'-chlorosulphonyl-                                                                        5-aminocarbonyl-6-hydroxy-1-                                                                   "                                            phenyl)-4,5-dichloro-6-                                                                       (4'-sulphophenylethyl)-3,4-                                   pyridazone      trimethylenepyrid-2-one                     40   "            6-methoxy-dct   "                "                          41   4,5-diaminobenzene-                                                                        6-(4'-sulphophenoxy)-dct                                                                      1-ethyl-6-hydroxy-3,4-                                                                         "                               1,3-disulphonic acid         pentamethylenepyrid-2-one                   42   "            6-phenoxy-dct   "                "                          43   "            6-methylamino-dct                                                                             "                "                          44   "            6-β-hydroxyethylamino-dct                                                                "                "                          45   2,4-diaminobenzene                                                                         6-(1',5'-disulphonaphth-                                                                      5-aminocarbonyl-1-n-butyl-6-                                                                   "                               sulphonic acid                                                                             7-ylamino)-dct  hydroxy-3,4-tetramethylene                                                    pyrid-2-one                                 46   "            6-(1',3',6'-trisulpho-                                                                        "                "                                            naphth-8-ylamino)-dct                                       47   4,6-diaminobenzene-                                                                        β-chloroethylsulphonyl-                                                                  5-aminocarbonyl-1-ethyl-6-                                                                     Greenish-                       1,3-disulphonic acid                                                                       endomethylene cyclohexane                                                                     hydroxy-3,4-tetramethylene                                                                     yellow                                       carbonyl chloride                                                                             pyrid-2-one                                 48   2,4-diaminobenzene                                                                         6-bis-β-hydroxyethyl-                                                                    "                "                               sulphonic acid                                                                             amino-dct                                                   49   "            6-N-methyl-N-β-                                                                          "                "                                            sulphoethylamino dct                                        50   4,6-diaminobenzene-                                                                        6-diethylamino-dct                                                                            6-hydroxy-1-methyl-3,4-                                                                        "                               1,3-disulphonic acid         tetramethylenepyrid-2-one                   51   "            6-(N-methyl-3'-sulpho-                                                                        6-hydroxy-1-methyl-3,4-                                                                        "                                            phenylamino)-dct                                                                              pentamethylenepyrid-2-one                   52   "            6-(4'-carboxyphenylamino)-                                                                    5-aminocarbonyl-1-ethyl-6-                                                                     "                                            dct             hydroxy-3,4-tetramethylene                                                    pyrid-2-one                                 53   2,4-diaminobenzene                                                                         6-(2'-methylphenylamino)-                                                                     aminocarbonyl-6-hydroxy-                                                                       "                               sulphonic acid                                                                             dct             1-(4'-sulphobenzyl)-3,4-                                                      tetramethylenepyrid-2-one                   54   4,6-diaminobenzene-                                                                        6-(4'-methoxyphenylamino)-                                                                    1-ethyl-6-hydroxy-3,4-                                                                         "                               1,3-disulphonic acid                                                                       dct             tetramethylenepyrid-2-one                   __________________________________________________________________________     dct = 2,4-dichloro-s-triazine                                            

EXAMPLE 55

2.68 parts of 1,3-phenylenediamine-4,6-disulphonic acid are condensedwith 1.95 parts of cyanuric chloride and the product is diazotized andcoupled with 2.36 parts of5-aminocarbonyl-3,4-tetramethylene-1-ethyl-6-hydroxypyrid-2-one asdescribed in Example 1.

1.85 parts of 4,4'-diaminostilbene-2,2'-disulphonic acid are dissolvedin 50 parts of water at pH 7 and added to the solution obtained inparagraph 1. The mixture is stirred at 30°-35° for 1 hour, the pH beingmaintained at 6-7 by occasional addition of 2N sodium carbonatesolution. The dyestuff is precipitated by salting to 15% w/v sodiumchloride, collected by filtration, washed with 50 parts of 20% brine anddried in vacuo at 40°. The product contains 2.1 moles of hydrolyzablechlorine per mole of dyestuff and when applied to cellulosic fibres inconjunction with an acid-binding agent, dyes the fibre in brilliantgreenish-yellow shades with good fastness to washing and light.

Further examples of the invention are obtained if the4,4'-diaminostilbene-2,2'-disulphonic acid in the above example bereplaced by equivalent amountsof4,4'-diaminodiphenylurea-2,2'-disulphonic acid Example56benzidine-2,2'-disulphonic acid Example572,6-diaminonaphthalene-4,8-disulphonic acid Example584,4'-diaminodiphenylether Example 594,4'-diaminodiphenylsulphoneExample 604,4'-diaminodiphenoxyethane-2,2'-disulphonic acid Example614,4'-diaminodiphenylsulphide-2,2'-disulphonic acid Example621,3-diaminobenzene-4,6-disulphonic acid Example 63

EXAMPLE 64

2.68 parts of 1,3-phenylenediamine-4,6-disulphonic acid are condensedwith 1.95 parts of cyanuric chloride and the product is diazotized andcoupled with 2.36 parts of5-aminocarbonyl-3,4-tetramethylene-1-ethyl-6-hydroxypyrid-2-one asdescribed in Example 1.

2.07 parts of 1,3-phenylenediamine-4-sulphonic acid are dissolved in 50parts of water at pH 7 and added to the solution obtained inparagraph 1. The mixture is stirred and slowly warmed to 30° at whichtemperature it is stirred for 1 hour. The pH is then raised to 6.5 bythe addition of sodium carbonate and stirred at 30°, pH 6-7 for afurther 1/2 hour. The solution is cooled to 0°-5° and added to a stirredsuspension of 2.75 parts of cyanuric chloride, 30 parts of ice, 30 partsof water and 1 part of dispersing agent. The mixture is stirred at 0°-5°for 8 hours, the pH being maintained at 6-7 by the occasional additionof 2N sodium carbonate. The mixture is screened and 10 parts of ammonialiquor (d 0.880) are added to the filtrate and the solution so obtainedstirred at 30° for 1 hour. The pH is reduced to 6.5 by the addition of2N hydrochloric acid and the dyestuff is precipitated by salting to 20%w/v sodium chloride. The product is filtered, washed with 30 parts of20% brine and dried in vacuo. Upon analysis it is found to contain 1.9parts of hydrolyzable chlorine per mole of dyestuff and, when applied tocellulosic fibres in conjunction with an acid-binding agent, to dye thefibres in brilliant greenish-yellow shades with good fastnessproperties.

Further examples of the invention are obtained if the1,3-phenylenediamine-4-sulphonic acid in the above example is replacedby an equivalent quantity of

    1,4-phenylenediamine-2-sulphonic acid                                                                    Example 65                                         1,4-phenylenediamine-2,5-disulphonic acid                                                                Example 66                                         1,3-phenylenediamine-4,6-disulphonic acid                                                                Example 67                                     

EXAMPLE 68

3.03 parts of 2-aminonaphthalene-1,5-disulphonic acid are stirred with75 parts of water and caustic liquor (s.g. 1.35) is added dropwise untilthe pH of the solution is 8. 5.25 Parts of 2N sodium nitrite solutionare added, the solution is cooled to 0°-5°, 75 parts of ice are addedand the mixture stirred vigorously while being acidified with 10 partsof hydrochloric acid (s.g. 1.18). The suspension is stirred at 0°-5° for1/2 hour and then the slight excess of nitrous acid is destroyed by theaddition of a few drops of a 10% aqueous solution of sulphamic acid. Thesuspension of the diazonium salt is added to a stirred solution of 2.29parts of 1-β-aminoethyl-6-hydroxy-3,4-tetramethylenepyrid-2-one in 75parts of 16% sulphuric acid. The mixture is stirred vigorously at 0°-5°while the pH is gradually raised to 2.5 by the dropwise addition ofammonia solution (s.g. 0.880). The yellow precipitate is filtered off,washed with 50 parts cold water and suspended in 100 parts of cold waterby stirring. Lithium hydroxide is added until a clear solution is formedof pH 11-12. This solution is added dropwise during 10 minutes to asuspension of cyanuric chloride prepared by adding a solution of 4 partsof cyanuric chloride in 15 parts of acetone to a stirred mixture of 50parts of ice, 50 parts of water and 1 part of dispersing agent. The pHof the mixture during the course of the addition of the dyebase solutionand for a further 1/2 hour is maintained at 9-10. At the end of thistime the pH is adjusted to 7 with dilute hydrochloric acid, a solutionof 3 parts of potassium dihydrogen orthophosphate and 1.5 parts ofdisodium hydrogen orthophosphate in 20 parts of water is added, and themixture is screened. The clear yellow filtrate is salted to 20% w/vsodium chloride and the product is collected by filtration, pasted with0.8 parts of potassium dihydrogen orthophosphate and 0.4 parts ofdisodium hydrogen orthophosphate and dried in vacuo. When applied tocellulosic fibres in conjunction with an acid binding agent, the fibresare dyed in greenish yellow shades fast to washing, chlorine and light.

The solution of 1-β-aminoethyl-6-hydroxy-3,4-tetramethylene pyrid-2-onein dilute sulphuric acid can be made as follows. 2.56 Parts of1-β-aminoethyl-5-cyano-3,4-tetramethylenepyrid-2-one and 15 parts of 80%sulphuric acid are stirred for 3 hours at 130°. After cooling thesolution is added to 60 parts of ice.1-β-aminoethyl-5-cyano-3,4-tetramethylenepyrid-2-one can be made in asimilar manner to that described for5-cyano-3,4-tetramethylene-1-ethyl-6-hydroxypyrid-2-one in Example 1, bysubstituting ethylamine with an equivalent quantity of ethylene diamine.

Further examples of the invention are described in the following tablein which compounds of the general formula ##SPC26##

in which the values of A, B, C, D, R and n are given in the appropriatecolumns, are acylated with the agent named in column 8 to give dyestuffshaving, on cellulose, greenish-yellow shades of similar fastnessproperties to the above example.

Compounds of formula (25) are obtained by following the procedureoutlined above namely coupling diazotized amines of formula ##SPC27##

with aminoalkyl pyridines of the formula ##SPC28##

themselves obtained by the method given above.

    Example                                                                            A   B   C   D         R     n Acylating Agent                            __________________________________________________________________________    69   H   H   SO.sub.3 H                                                                        CH.sub.2 CH.sub.2                                                                       H     3 6-(4'-sulphophenoxy)-dct                   70   "   "   H   "         "     2 6-(3',5'-disulphophenylamino)-dct          71   SO.sub.3 H                                                                        "   SO.sub.3 H    "     1 6-amino-dct                                72   H   SO.sub.3 H                                                                        H   CH.sub.2 CH.sub.2                                                                       "     2 cyanuric chloride                          73   "   "   "   "         CH.sub.2 CH.sub.2 OH                                                                2 6-(3'-sulphophenylamino)-dct               74   "   H   SO.sub.3 H                                                                        CH.sub.2 CH.sub.2 CH.sub.2                                                              H     2 6-(4'-sulphophenylamino)-dct               75   "   "   H   "         "     3 6-(2'-methyl-5'-sulphophenylamino)-dct                                        2                                          76   SO.sub.3 H                                                                        "   SO.sub.3 H                                                                        CH.sub.2 CH.sub.2                                                                       CH.sub.2 CH.sub.2 OH                                                                3 6-(1'-sulphonaphth-6'-ylamino)-dct         77   "   "   "   "         H     2 6-(2'-sulphonaphth-6'-ylamino)-dct         78   H   SO.sub.3 H                                                                        H   CH.sub.2 CH.sub.2 CH.sub.2                                                              CH.sub.3                                                                            2 6-(N'-ω-methanesulphonylphenylami                                       no)-dct                                    79   "   H   "   "         H     2 6-(1' ,3',6'-trisulphonaphth-8'-ylamino                                       )-dct                                      80   "   "   SO.sub.3 H                                                                        CH.sub.2 CH.sub.2                                                                       "     2 6-methoxy-dct                              81   SO.sub.3 H                                                                        "   "   "         "     1 6-isopropoxy-dct                           82   H   SO.sub.3 H                                                                        H   CH.sub.2 CH.sub.2                                                                       CH.sub.2 CH.sub.2 OH                                                                2 6-[3'-(6"-amino-4"-chloro-s-triazin-2"-                                       ylamino)-                                                                     4'-sulphophenylamino]-dct                  83   "   H   SO.sub.3 H                                                                        "         H     2 6-[3'- 4"-chloro-6"-(3"'-sulphophenylam                                       ino)-s- -       triazin-2"-ylamino                                            -4'-sulphophenylamino]-dct                 84   SO.sub.3 H                                                                        "   "   CH.sub.2 CH.sub.2 CH.sub.2                                                              CH.sub.3                                                                            3 6-[4'-(4"-chloro-6"-methoxy-s-triazin-2                                       "-yl-                                                                         amino)-3'-sulphophenoxy]-dct               85   H   SO.sub.3 H                                                                        H             H     2 6-[3'-(4",6"-dichloro-s-triazin-2'-ylam                                       ino)-                                                                         4',6'-disulphophenylamino]-dct (1/2                                           mole)                                      86   "   H   SO.sub.3 H                                                                        CH.sub.2 CH.sub.2                                                                       "     2 6-[4"-(4",6"-dichloro-s-triazin-2"'-yla                                       mino)-                                                                        2',2"-disulphostilbene-4'-amino]-dct                                          (1/2 mole)                                 87   "   "   "   "         CH.sub.2 CH.sub.2 OH                                                                2 6-[4"-(4",6"-dichloro-s-triazin-2"'-yla                                       mino)-                                                                        2,2"-disulphodiphenylurea-4'-amino]-dct                                        (1/2 mole)                                88   SO.sub.3 H                                                                        "   "   CH.sub.2 CH.sub.2 CH.sub.2                                                              H     2 2,4,6-trichloropyrimidine                  89   H   SO.sub.3 H                                                                        H   CH.sub.2 CH.sub.2                                                                       CH.sub.2 CH.sub.2 OH                                                                1 tetrachloropyrimidine                      90   "   "   "   "         H     1 2,4,6-tribromopyridine                     91   "   "   "   "         "     2 5-cyano-2,4,6-trichloropyrimidine          92   SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        "         H     2 5-methyl-2,4,6-trichloropyrimidine         93   H   "   "   "         "     2 5-nitro-2,4,6-trichloropyrimidine          94   H   H   SO.sub.3 H                                                                        CH.sub.2 CH.sub.2                                                                       H     2 5-chloro-2,4,6-trifluoropyrimidine         95   "   "   "   "         "     2 4,5-dichloro-6-methyl-2-methylsulphonyl                                        pyrimidine                                96   SO.sub.3 H                                                                        "   "   "         CH.sub.2 CH.sub.2 OH                                                                1 5-ethoxycarbonyl-2,4-dichloropyrimidine    97   "   "   "   "         "     1 2,4-dichloropyrimidine-5-carbonyl                                             chloride                                   98   H   "   "   CH.sub.2 CH.sub.2 CH.sub.2                                                              H     2 2,4-dichloropyrimidine-5-sulphonyl                                            chloride                                   99   SO.sub.3 H                                                                        "   "   CH.sub.2 CH.sub.2                                                                       CH.sub.3                                                                            2 2,3-dichloroquinoxalin-5-sulphonyl                                            chloride                                   100  H   SO.sub.3 H                                                                        H   "         H     3 2,3-dichloroquinoxalin-6-sulphonyl                                            chloride                                   101  "   "   "             "     1 2,3-dichloroquinoxalin-6-carbonyl                                             chloride                                   102  "   H   SO.sub.3 H                                                                        CH.sub.2 CH.sub.2                                                                       CH.sub.2 CH.sub.2 OH                                                                1 2,3-dichloroquinoxalin-5-carbonyl                                             chloride                                   103  SO.sub.3 H                                                                        "   "   "         "     2 2,4-dichloroquinazolin-6-sulphonyl                                            chloride                                   104  "   "   "   (CH.sub.2).sub.4                                                                        H     2 2,4-dichloroquinazolin-6-carbonyl                                             chloride                                   105  H   "   "   (CH.sub.2).sub.5                                                                        "     3 2,4-dichloroquinazolin-7-carbonyl                                             chloride                                   106  "   "   "   (CH.sub.2).sub.6                                                                        "     2 2,4-dichloroquinazolin-7-sulphonyl                                            chloride                                   107  "   "   "   CH.sub.2 CH.sub.2                                                                       "     2 2,4,6-trichloroquinazolin-7-sulphonyl                                         chloride                                   108  SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        CH.sub.2 CH.sub.2                                                                       CH.sub.2 CH.sub.2 OH                                                                2 2,4,6-trichloroquinazolin-8-sulphonyl                                         chloride                                   109  H   SO.sub.3 H                                                                        H   CH.sub.2 CH.sub.2 CH.sub.2                                                              H     2 2,4,7-trichloroquinazolin-6-sulphonyl                                         chloride                                   110  "   "   "   "         CH.sub.3                                                                            1 2,4,8-trichloroquinazolin-6-sulphonyl                                         chloride                                   111  "   "   "   CH.sub.2 CH.sub.2                                                                       H     2 1,4-dichlorophthalazin-6-carbonyl                                             chloride                                   112  "   H   SO.sub.3 H                                                                        "         "     2 β-(4',5'-dichloropyridazonyl-1-)pr                                       opionyl chloride                           113  SO.sub.3 H                                                                        "   "   "         "     2 1-(4'-chloroformylphenyl)-4,5-dichloro-                                       6-pyridazone                               114  "   "   "   "         "     2 1-(4'-chlorosulphonylphenyl)-4,5-dichlo                                       ro-6-                                                                         pyridazone                                 115  H   "   "   "         "     2 6-bis-β-hydroxyethylamino-dct         116  "   SO.sub.3 H                                                                        H   "         CH.sub.2 CH.sub.2 OH                                                                2 6-N-methyl-N-β-sulphoethylamino-dc                                       t                                          117  "   "   "   CH.sub.2 CH.sub.2 CH.sub.2                                                              CH.sub.3                                                                            1 6-diethylamino-dct                         118  SO.sub.3 H                                                                        H   SO.sub.3 H                                                                        CH.sub.2 CH.sub.2                                                                       H     2 6-(N-methyl-3'-sulphophenylamino)-dct      119  "   "   "   (CH.sub.2).sub.6                                                                        "     2 6-(4'-carboxyphenylamino)-dct              120  "   "   "   CH.sub.2 CH.sub.2                                                                       "     2 6-(2'-methylphenylamino)-dct               121  "   "   "   "         "     2 6-(4'-methoxyphenylamino)-dct              122  H   SO.sub.3 H                                                                        H             H     3 6-(4'-chlorophenylamino)-dct               123  "   "   "   CH.sub.2 CH.sub.2                                                                       CH.sub.2 CH.sub.2 OH                                                                2 6-β-hydroxyethylamino-dct             124  "   H   SO.sub.3 H                                                                        "         H     2 6-γ-methoxypropylamino-dct           125  "   "   "   "         "     2 6-(4'-β-sulphatoethylsulphonylphen                                       ylamino)-dct                               126  "   "   "   "         "     2 6-(3'-β-sulphatoethylsulphonylphen                                       ylamino)-dct                               127  "   "   "   "         "     2 5-bromo-2,4,6-trichloropyrimidine          128  "   "   "   "         "     2 2,2,3,3-tetrafluorocyclobutyl carbonyl                                        chloride                                   129  SO.sub.3 H                                                                        "   "   "         "     2 2,3,3-trifluorocyclobut-1-enyl                                                carbonyl chloride                          130  H   SO.sub.3 H                                                                        H   "         "     2 β-(2,2,3,3-tetrafluorocyclobutyl)a                                       cryloyl chloride                           131  "   "   "   CH.sub.2 CH.sub.2 CH.sub.2                                                              "     2 β-(2,3,3-trifluorocyclobut-1-enyl)                                       acryloyl chloride                          132  "   "   "   CH.sub.2 CH.sub.2                                                                       "     2 β-chloroethylsulphonylendomethylen                                       e cyclohexane                                                                 carbonyl chloride                          133  "   H   SO.sub.3 H                                                                        "         CH.sub.2 CH.sub.2 OH                                                                2 6-anilino-dct                              134  SO.sub.3 H                                                                        "   "   "         H     2 2-chlorobenzthiazole-6-carbonyl                                               chloride                                   __________________________________________________________________________     dct = 2,4-dichloro-s-triazine                                            

EXAMPLES 135-143

6.7 Parts of the dyestuff made as described for Example 68 are dissolvedin 200 parts of water at 35°, pH 7. To the stirred solution is added asolution of 1.8 parts of 4,4'-diaminodiphenyl sulphide-2,2'-disulphonicacid in 50 parts of water at 35°, pH 7. The solution is stirred at35°-40°, pH 6.5 - 7.5 for 2 hours, and the product isolated by coolingand salting to 20% w/v sodium chloride. The product is collected byfiltration and dried. When applied to cellulosic fibres in conjunctionwith an acid binding agent, it dyes the fibres in greenish yellow shadesfast to washing, light and chlorine.

Further examples of the invention are obtained if the4,4'-diaminodiphenylsulphide-2,2'-disulphonic acid in the above examplecan be replaced by equivalent quantities of

    4,4'-diaminodiphenylurea-2,2'-disulphonic acid                                                          Example 136                                         benzidine-2,2'-disulphonic acid                                                                         Example 137                                         2,6-diaminonaphthalene-4,8-disulphonic acid                                                             Example 138                                         4,4'-diaminodiphenylether Example 139                                         4,4'-diaminodiphenylsulphone                                                                            Example 140                                         4,4'-diaminodiphenoxyethane-2,2'-disulphonic acid                                                       Example 141                                         4,4'-diaminostilbene-2,2'-disulphonic acid                                                              Example 142                                         1,3-diaminobenzene-4,6-disulphonic acid                                                                 Example 143                                     

We claim:
 1. A dyestuff of the formula ##SPC29##wherein m is 1, 2 or 3;R⁹ is selected from the group consisting of ##SPC30##wherein n is 0 or 1and R" is hydrogen or lower alkyl and ##SPC31## wherein p is 1, 2 or 3;R¹⁰ is selected from the group consisting of C₁₋₆ alkyl, benzyl,sulphobenzyl, phenylethyl, sulphophenylethyl, ##EQU13## wherein r is 2to 6, ##SPC32##wherein R" has the meaning given above and the dyestuffas a whole contains only one group represented by Z; and Z is acellulose-reactive group selected from the group consisting of
 2. 2.3-dichloroquinoxalin-5-sulphonyl,2,3-dichloroquinoxalin-5-carbonyl,2,3-dichloroquinoxalin-6-sulphonyl, 2,3-dichloroquinoxalin-6-carbonyl,2,4-dichloroquinazolin-6-sulphonyl, 2,4-dichloroquinazolin-6-carbonyl,2,4-dichloroquinazolin-7-sulphonyl,2,4,6-trichloroquinazolin-7-sulphonyl,2,4,6-trichloroquinazolin-8-sulphonyl,2,4,7-trichloroquinazolin-6-sulphonyl,2,4,8-trichloroquinazolin-6-sulphonyl,1,4-dichlorophthalazin-6-carbonyl, β(4,5-dichloropyridazon-1-yl)propionyl, 2.4-dichloropyrimidin-5-carbonyl,4-(4',5'-dichloropyridazon-1-yl)phenylsulphonyl, 2,4-dichloropyrimid-6-yl, 2,4,5-trichloropyrimid-6-yl,2,4-dichloro-5-cyanopyrimid-6-yl, 2,4-difluoro-5-chloropyrimid-6-yl,5-chloro-6-methyl-2-methylsulphonylpyrimid-4-yl,2,4-dichloro-5-bromopyrimid-6-yl, 2,4-dichloropyrimidin-5-sulphonyl,2,2,3,3-tetrafluorocyclobutylcarbonyl, 2,3,3-trifluorocyclobut-1-enylcarbonyl, β-(2,2,3,3-tetrafluorocyclobutyl) acryloyl,β-(2,3,3-trifluorocyclobut-1-enyl) acryloyl,2-chlorobenzthiazol-6-carbonyl, ##EQU14## wherein X is Cl, NH₂, loweralkoxy, phenoxy, sulphophenoxy, lower alkylamino, di(lower alkyl)amino,##SPC33##wherein p is 1, 2 or 3, ##SPC34## wherein p is 1, 2 or 3,##SPC35## ##SPC36## wherein X¹ is CH₃, Cl, OCH₃ or CO₂ H and q is 1 or2, ##SPC37## wherein q and X have the meanings given above, and##EQU15## wherein Ar is the N,N'-divalent radical of a diamine selectedfrom the group consisting of 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylsulphone, 4,4'-diaminodiphenoxyethane-2,2'-disulphonic acid,2,6-naphthalene-4,8-disulphonic acid, benzidine-2,2'-disulphonic acid,4,4'-diamino-diphenylurea-2,2'-disulphonic acid,4,4'-diamino-stilbene-2,2'-disulphonic acid,1,3-diaminobenzene-4,6-disulphonic acid and4,4'-diaminodiphenylsulphide-2,2'-disulphonic acid, and D is a secondmonovalent monoazo entity of the formula ##SPC38## wherein m is 1, 2 or3; R⁹ is ##SPC39## wherein n and R" have the meaning given above or##SPC40## wherein p has the meaning given above; and R₁₀ is selectedfrom the group consisting of C₁₋₆ alkyl, benzyl, sulphobenzyl,phenylethyl, sulphophenylethyl, ##EQU16## where r is 2 to 6, ##SPC41##wherein R" has the meaning given above.
 2. A dyestuff as claimed inclaim 1 in which R⁹ is ##SPC42##and R¹⁰ is selected from the groupconsisting of C₁₋₆ alkyl, benzyl, sulphobenzyl, phenylethyl andsulphophenylethyl, where n, R¹¹ and Z have the meanings given inclaim
 1. 3. A dyestuff as claimed in claim 2 of the formula##SPC43##wherein m, n, R¹⁰ and R¹¹ have the meanings given in claim 2.4. A dyestuff as claimed in claim 6 in which R⁹ is ##SPC44##and R¹⁰ isselected from the group consisting of ##EQU17## ##SPC45## where p, r,R¹¹ and Z have the meanings given in claim
 1. 5. A dyestuff as claimedin claim 4 of the formula ##SPC46##wherein R¹² is selected from thegroup consisting of ##EQU18## ##SPC47## ##SPC48## in which the CH₂ groupis joined to the nitrogen of the pyridone ring, m, r, p and R" have themeanings given in claim 4 and Ar is the N,N'-divalent radical of adiamine selected from the group consisting of4,4'-diamino-diphenylether, 4,4'-diamino diphenylsulphone,4,4'-diamino-diphenoxyethane-2,2'-disulphonic acid,2,6-naphthalene-4,8-disulphonic acid, benzidine-2,2'-disulphonic acid,4,4'-diaminodiphenylurea-2,2'-disulphonic acid,4,4'-diaminostilbene-2,2'-disulphonic acid,1,3-diaminobenzene-4,6-disulphonic acid and4,4'-diaminodiphenylsulphide-2,2'-disulphonic acid.